Field of the Invention
This invention relates to rapid set, medium set, and
slow set anionic emulsions prepared from straight bitumen
or bitumen modified by the incorporation of polymers such
as styrene butadiene rubbers (SBR), styrene block
copolymers (SBS), ethylene vinyl acetate copolymers (EVA),
and other suitable modifiers. The invention also relates
to emulsions modified by the incorporation of solvents
(such as diesel oil or kerosene) or by the addition of
polymer latices (such as SBR-latex or natural rubber
latex). More particularly, the invention relates to
improved methods for enhancing adhesion between asphalt and
aggregate in anionic solventless and solvent-containing
bituminous emulsions wherein the emulsifiers are alkali
earth salts of tall oil fatty acids, fortified tall oil
fatty acids, tall oil rosin and fortified rosin as well as
combinations of kraft lignin and nonionic emulsifiers. The
adhesion promoters utilized in these improved methods are
the reaction products of styrene (α-methyl styrene)-acrylic
(metacrylic) acid polymers with polyalkylene amines.
Further improvement can be obtained by using tall oil fatty
acid or fortified tall oil fatty acids as co-reactants in
the production of the polyamidoamine products.
BACKGROUND OF THE INVENTION
In paving operations, three main practices are
employed to achieve thorough mixing of bitumen and
aggregate:
(1) mixing of free flowing heated asphalt (asphalt
cement) with pre-dried aggregate, (2) mixing pre-dried aggregate with asphalt diluted
with a hydrocarbon solvent (cutback asphalt,
cutter stock) at ambient or slightly elevated
temperatures, and (3) mixing aggregate with asphalt emulsions, e.g.,
oil in water emulsions, obtained by vigorous
agitation of asphalt and water in the presence of
an emulsifying agent.
The escalating costs of energy and hydrocarbon
solvents coupled with a heightened environmental awareness
have stimulated increases in the use of emulsified asphalts
in the road paving industry. The type of emulsifier
employed is determined by the desired application of the
asphalt emulsion. For rapid set emulsions (mainly used for
chip sealing) sodium soaps of tall oil are commonly
utilized. For medium set emulsions (applied in cold mixes
of virgin aggregate or reclaimed asphalt pavement) higher
concentrations of tall oil or modified tall oil soaps are
generally being used with and without the addition of
moderate amounts of hydrocarbon solvent. Slow set
emulsions with good mix stability in the presence of fine
graded aggregate are usually based on vinsol (a by-product
of the wood rosin manufacture), on fortified tall oil rosin
in combination with kraft lignin or lignosulfonates, and
combinations of kraft lignin or lignosulfonates with
nonionic emulsifiers from the class of ethoxylated
alkylphenols, ethoxylated linear or branched fatty alcohols
and of ethylene oxide-propylene oxide-block co-polymers.
In anionic emulsions the asphalt droplets are stabilized by
anionic surfactants (wherein their negatively-charged
surface migrates to the anode when an electric field is
applied).
In the case of rapid set emulsions (mainly used for
repair work of old wearing courses) the emulsion is applied
on the existing surface and aggregate is spread on top.
After the water of the emulsion has evaporated, an intimate
matrix of asphalt and stone with good load bearing capacity
is formed. The road can be re-opened to traffic shortly
after application of the seal. Medium set emulsions are
commonly being mixed with aggregate in a pug mill prior to
being used in road construction. The incorporation of
solvent allows the mixes to be stock piled prior to use.
The mixes are prepared in central mixing plants and
transported to the job sites or are generated "in-place".
Slow set emulsions are being applied where good penetration
and wetting is necessary. Mixes with high loadings of
fines, base stabilization and tack coat are the main
applications.
Anionic emulsions are taught by Mertens in U.S. Patent
No. 3,062,829 to be prepared via the use of alkali
hydroxide which saponify the surface active acids naturally
occurring in asphalt. These emulsions contain high
molecular weight polyamides (Versene) as viscosity reducers
and adhesion promoters. In U.S. Patent No. 3,108,971 to
Mertens anionic emulsions of the same type are improved
with the addition of alkanol amines lacking lipophilic
characteristics. Lignin amines are taught by Borgfeldt in
U.S. Patent No. 3,123,569. Quick setting emulsions
obtained from highly acidic asphalts using lithium
hydroxide are disclosed by Mertens in U.S. Patent No.
3,240,716. Montgomery and Pitchford teach the alkali metal
salts of complex polynuclear aromatic polycarboxylic acids
as anionic emulsifiers in U.S. Patent No. 3,344,082. Heinz
in U.S. Patent No. 3,006,860 employs alkali metal soaps of
higher fatty acids such as those found in tall oil. In
U.S. Patents Nos. 3,956,002 and 4,088,505 Moorer teaches
anionic emulsifiers consisting of alkali lignin or
oxygenated alkali lignin, an ethylene oxide adduct of
alkylphenol and up to 10% by weight of sodium borate.
Detroit describes in U.S. Patent No. 4,293,459 combinations
of partially desulfonated oxygenated lignosulfonates and
nonionic surfactants. Schilling et al. disclose the alkali
soaps of maleated or fumarated tall oil fatty acids or
rosin, of DIACID® 1550 and of sulfonated tall oil fatty
acid as emulsifiers for anionic high float emulsions in
U.S. Patent No. 4,676,927 and the use of carboxyethylated
modified tall oil amidoamines as emulsifiers for anionic
slurry seals in U.S. Patent No. 4,561,901. Ferm in U.S.
Patent No. 3,740,344 teaches the preparation of quick set
anionic slurry seal compositions by applying a combination
of aryl alkyl sulfonucts of alkyl phenols and of fatty
alcohols. Schreuders in U.S. Patent No. 3,615,796 teaches
the use of petroleum sulfonates. A combination of sodium
lignate or lignosulfonate and saponified tall oil or rosin
is disclosed in U.S. Patent No. 3,594,201 by Sommer and
Evans. In U.S. Patent No. 3,350,321 Conn describes the use
of alkyl or alkoxy alkyl phosphoric acid salts as
emulsifiers for asphalt.
Anionic emulsions are generally prepared at emulsifier
concentrations of 0.2-10.0% based on 100% activity,
preferentially at 0.2 to 2.0%. The pH range is 7 to 14,
preferentially at 10 to 12 in the case of tall oil and
rosin soaps. The advantage of anionic emulsions lies in
the relatively low cost of tall oil based emulsifiers. The
disadvantage is the low bond strength of asphalt to
aggregate once the emulsion has dried and formed a film of
asphalt on the surface of the aggregate. As most of the
aggregates are negatively charged, the electrostatic
repulsion between the negatively charged asphalt and the
negatively charged stones causes inferior adhesion. Highly
acidic aggregates such as quartzite, granite, rhyolite and
many of the sedimentary, metamorphic and igneous rocks are
considered responsible for the existing bitumen-stripping
problem. This problem is also encountered in hot mix
applications and when cut back asphalts are being used.
The quality of the road surface is generally dependent
upon the strength of the bonds between the asphalt and the
aggregate after curing of the composition. Poor service
performance is due to poor adhesion, which results in
asphalt stripping off the aggregate surface. Asphalt
compositions also have relatively poor adhesion to
aggregate in the presence of water. Since the aggregate is
preferentially wetted by water, the eventual penetration of
water into the composition reaches the aggregate and
interferes with the bond between aggregate and asphalt.
The result of this stripping is flaked pavement and the
formation of pot holes.
To reduce water-induced debonding of asphalt from the
stone surface, in many cases surface-active amines or
diamines are added to the asphalt. Generally, anti-stripping
agents or adhesion promoters are introduced into
the asphalt prior to the asphalt being mixed with the
aggregate. In the case of anionic asphalt emulsions it is
advantageous to add the additive to the emulsion to prevent
degradation at the high pH values. The patent literature
sets forth a large number of compounds which can be used to
improve adhesion of asphalt to aggregate. These include
ethylene oxide condensates of long chain alkyl triamines
(U.S. Patent No. 3,615,797), alkoxylated amines and their
salts (U.S. Patent No. 3,347,690), and reaction products of
ozonized unsaturated fatty acids with polyalkylene amines
(U.S. Patents Nos. 3,246,008 and 3,245,451). Other
additives are based on fatty carboxylic chromites (U.S.
Patent No. 3,963,509), on combinations of epoxy resins and
onium borates (U.S. Patent No. 3,947,395), on tall oil
alkanol amines and amido amines (U.S. Patents Nos.
2,679,462 and 4,806,166), on fatty ether amines in
combination with alkanol amines (U.S. Patent No.
3,928,061), and on fatty acid amido amine soaps (U.S.
Patents Nos. 2,426,220, 2,891,872 and 3,230,104).
Aminoalkyl polyalkoxysilanes are disclosed in U.S. Patent
No. 3,861,933; and condensation products of amines,
polyamines, and amides with formaldehyde are taught in U.S.
Patent No. 4,639,273. Mannich reaction products of
polyamines with formaldehyde and alkylphenols are described
in U.S. Patent No. 4,789,402, and ethoxylated
hexamethylene-diamines and their derivatives are taught in
European Patent Application No. 0 077 632 (82305420.0).
Fatty primary, secondary and tertiary amines and
imidazolines, their reaction products with various acids
(including fatty acids), metal soaps, and several other
compounds including rosin reaction products are described
in U.S. Patent No. 3,868,263.
One relatively inexpensive class of adhesion promoters
which have shown promise for use in hot mix and in cut back
asphalts are tall oil-based polyethylene amine condensation
products. However, a major problem exists with such
adhesion promoters in that their adhesion efficiencies are
not high enough to obtain satisfactory results when they
are utilized in anionic emulsions. It is, therefore, the
object of this invention to solve this problem by
disclosing an improved method for enhancing adhesion
between asphalt and aggregate in anionic bituminous
emulsions.
SUMMARY OF THE INVENTION
The objective of this invention is met by adding a
polyamidoamine adhesion promoter to the anionic bituminous
emulsion. Suitable polyamidoamine adhesion promoters are
produced by reacting a styrene-acrylic acid copolymer
(alone or blended with a tall oil fatty acid or rosin) in
a condensation reaction with a polyamine (or blends of
polyamines). A preferred method utilizes adhesion
promoters produced by substituting up to 90% of the
styrene-acrylic acid copolymer with a member selected from
the group consisting of C8-C20 fatty acids, C9-C22 modified
fatty acids of rosin, C23-C24 modified rosins, or
combinations thereof.
The improved methods for enhancing adhesion between
asphalt and aggregate are effective even when utilized with
traditionally recalcitrant, highly acidic aggregates. The
adhesion promoting effects produced via the addition of
these products are primarily due to the products' ability
to migrate to the asphalt/aggregate interphase, where they
hydrophobize the aggregate surface and render it water
repellent. In addition, these products also increase
adhesion by neutralizing some of the negative charges
introduced into the asphalt by the anionic character of the
emulsifier.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The improved method for enhancing adhesion between
asphalt and aggregate in anionic bituminous (asphalt)
emulsions comprises the addition to the emulsion of a
composition comprising the polyamidoamine condensation
reaction products of:
(A) 20-80 wt.% of a copolymer, formed by reacting
(1) 1-99 wt.% of a member selected from the
Group consisting of α-methyl styrene,
styrene, and combinations thereof, with (2) 99-1 wt.% of a member selected from the
group consisting of acrylic acid, metacrylic
acid, alkyl esters of acrylic acid, alkyl
esters of metacrylic acid, and combinations
thereof; and (B) 80-20 wt.% of a polyamine.
The process of producing these adhesion promoters
(which are also effective as corrosion inhibitors for steel
exposed to highly acidic environments) was disclosed by
Schilling in U.S. Patent No. 5,516,826. First, in a
polymerization reaction (α-methyl) styrene reacts with a
member selected from the group consisting of acrylic acid,
metacrylic acid, their respective alkyl esters, and
combinations thereof to form a styrene-acrylic acid
copolymer. This copolymer is subsequently reacted in a
condensation reaction with a polyamine or blend of
polyamines to form the polyamidoamine adhesion promoter.
These promoters do not contain any unreacted carboxylic
acid groups. This chemical reaction scheme is shown in
Figure 1 below.
A preferred method for enhancing adhesion between
asphalt and aggregate in anionic bituminous (asphalt)
emulsions comprises the addition to the emulsion of a
composition comprising the polyamidoamine condensation
reaction products of:
(A) 30-70 wt.% of a copolymer, formed by reacting
(1) 20-80 wt.% of a member selected from the
group consisting of α-methyl styrene, styrene,
and combinations thereof, with (2) 80-20 wt.% of a member selected from the
group consisting of acrylic acid, metacrylic
acid, alkyl esters of acrylic acid, alkyl esters
of metacrylic acid, and combinations thereof; and (B) 70-30 wt.% of a polyamine.
The ratio of (α-methyl) styrene to acrylic acid (or
metacrylic acid) required to yield the desired styrene -
acrylic acid copolymers ranges from about 1:1 to 3:1.
These copolymers are produced by heating in the presence of
a suitable radical initiator the desired mixture of (α-methyl)styrene
and acrylic acid (or metacrylic acid) to a
temperature in the range of about 180-270°C for a time
sufficient for the polymerization reaction to occur
(usually about 1 to 20 min). This polymerization reaction
is described in U.S. Pat. No. 4,546,160 by Brandt et al.
Styrene-acrylic acid copolymers suitable for the practice
of this invention have number average molecular weights in
the range of about 1,000 to about 10,000. The ratio of
styrene-acrylic acid copolymer to polyamine required to
produce the desired polyamidoamine adhesion promoter is 1:1
to 2:1. These promoters are obtained by heating the
desired mixture of styrene-acrylic acid copolymer and
polyamine to a temperature in the range of about 180-260°C
for a time sufficient for the condensation reaction to
occur (usually about 2 to 8 hours).
A more preferred method for enhancing the adhesion of
asphalt to aggregate in anionic bituminous emulsions
comprises the addition to the emulsion of a composition
comprising the polyamidoamine condensation reaction
products of:
(A) 20-80 wt.% of a mixture containing:
(1) 20-80 wt.% of a copolymer formed by reacting
(a) 1-99 wt.% of a member selected from the
group consisting of α-methyl styrene,
styrene, and combinations thereof, with (b) 99-1 wt.% of a member selected from the
group consisting of acrylic acid,
metacrylic acid, alkyl esters of
acrylic acid, alkyl esters of
metacrylic acid, and combinations
thereof; and (2) 80-20 wt.% of a member selected from the
group consisting of rosin, C23-C24 modified rosins,
C8-C20 fatty acids, C9-C22 modified fatty acids,
and combinations thereof; and (B) 80-20 wt.% of a polyamine.
The most preferred method for enhancing the adhesion
of asphalt to aggregate in anionic bituminous emulsions
comprises the addition to the emulsion of a composition
comprising the polyamidoamine condensation reaction
products of:
(A) 30-70 wt.% of a mixture containing:
(1) 20-80 wt.% of a copolymer formed by reacting
(a) 20-80 wt.% of a member selected from the
group methyl styrene, styrene, and combinations
thereof, with (b) 80-20 wt.% of a member selected from the group
consisting of acrylic acid, metacrylic acid, alkyl
esters of acrylic acid, alkyl esters of metacrylic
acid, and combinations thereof; and (2) 80-20 wt.% of a member selected from the group
consisting of rosin, C23-C24 modified rosins, C8-C20
fatty acids, C9-C22 modified fatty acids, and
combinations thereof; and (B) 70-30 wt.% of a polyamine.
Adhesion promoters suitable for use in these preferred
methods are produced by replacing up to 80% of the styrene-acrylic
acid copolymer with a member selected from the
group of rosin (i.e. resin acid), C23-C24 modified rosins, C8-C20
fatty acids, C9-C22 modified fatty acids, and combinations
thereof. Fatty acids which are suitable for the practice
of this invention have number average molecular weights in
the range of about 100 to about 350. Sources of such
suitable fatty acids include various animal fats and
vegetable oils, glycerides, tall oil fatty acids, and
petroleum-derived fatty acids. The term "tall oil fatty
acid" refers generally to the class of products containing
90% or more fatty acids which are obtained by fractionation
of crude tall oil. The fatty acids are primarily a
combination of oleic and linoleic acids, with small amounts
of saturated and other unsaturated fatty acids. Common
impurities include rosin and neutral materials.
Modified C9-C22 fatty acids suitable for the practice of
this invention have number average molecular weights in the
range of about 200 to about 470 and are produced by
reacting in a Diels-Alder cycloaddition polyunsaturated
fatty acids (such as linoleic acid) with fumaric acid,
maleic anhydride, itaconic acid, metacrylic acid, acrylic
acid, or citric acid (after dehydration and
decarboxylation) to produce cyclic polycarboxylic acids.
The Diels-Alder reaction is described in the commonly
assigned U.S. Patent No. 5,194,640 to Cosgrove et al.
Reaction products of unsaturated fatty acid such as
oleic acid or nonconjugated linoleic acid with maleic
anhydride via the "ene"-reaction are also suitable as C22-fatty
acid anhydrides. These types of tall oil fatty acid-derived
anhydrides are described in U.S. Patent No.
3,451,958 by Riedeman et al. Rosin suitable for the
practice of this invention have number average molecular
weights in the range of about 300 to about 350 and include
wood rosin, gum rosin, and tall oil rosin. Modified C23-C24
rosins suitable for the practice of this invention have
number average molecular weights in the range of about 370
to about 470 and are produced by reacting in a Diels-Alder
cycloaddition rosin with fumaric acid, maleic anhydride,
itaconic acid, metacrylic acid, acrylic acid, or citric
acid after dehydration and decarboxylation to produce
polycyclic polycarboxylic acid and acid anhydrides. This
Diels-Alder reaction is described in the commonly assigned,
U.S. Patent No. 5,208,319 to Schilling.
Polyamines which are suitable for the use in these
methods have a number average molecular weight in the range
of about 60 to about 1,000 and include many amines capable
of forming an amidoamine when reacted with the polymer.
Such polyamines include, but are not limited to, the
following: aminoethylethanolamine, aminoethylpiperazine,
diethylenetri-amine, triethylenetetramine,
tetraethylenepentamine, hexaethyleneheptamine, bis-amino-propylamine,
pentamethylenediamine, hydroxyethylpiperazine,
bis-hexamethylenetriamine, homologs, and combinations
thereof.
Radical initiators which are suitable for the use in
the above noted polymerization reactions include heat
sensitive organic peroxides and azo compounds, and the
like.
For application purposes it is preferred to produce
adhesion promoters which are liquid in form. Therefore it
may be necessary to adjust the viscosities of certain
formulations by the addition of a solvent (a process well
within the ability of a skilled artisan). Solvents which
are suitable for use in the present methods include, but
are not limited to, the following: ethylene glycol,
diethylene glycol, polyethylene glycol, propylene glycol,
alkanolamines, and combinations thereof. Preferred
alkanolamines suitable for use as a solvent include
monoethanolamine, diethanolamine, triethanolamine,
combinations thereof, and the like.
The following examples are provided to further
illustrate the present invention and are not to be
construed as limiting the invention in any manner.
EXAMPLE 1
A polyamidoamine adhesion promoter was produced via
the following method. A clean 2L three-necked flask
equipped with stirrer, thermometer, and reflux condenser
with a Dean Stark trap was charged with 50 parts by weight
of a polyamine blend mainly consisting of triethylene
tetramine and aminoethyl piperazine and 100 parts by weight
of diethylene glycol at room temperature. This mixture was
heated to 50 -100° C., at which time 50 parts by weight of
JONCRYL® 678 (a styrene-acrylic resin manufactured by S.C.
Johnson, Inc.) were slowly added to the flask while
agitating. The mixture was heated at 240-250°C. for six
hours before being allowed to cool. The resulting adhesion
promoter is hereafter referred to as AP#1.
EXAMPLE 2
A preferred adhesion promoter was produced via the
following method. To the same type of reaction apparatus
described in Example 1 above was charged 100 parts by
weight of polyamine blend (mainly consisting of triethylene
tetramine and aminoethyl piperazine) and 75-100 parts by
weight of a tall oil fatty acid blend containing less than
5% rosin. The addition occurred at room temperature and
resulted in an exothermic reaction. The reaction mixture
was heated to 100-120°C and 50-75 parts by weight of
JONCRYL® 680 (a styrene-acrylic resin manufactured by
S.C.Johnson) was slowly added with agitation to the flask
and heating to 240-260°C resumed. After a reaction time of
six hours at this temperature the products were allowed to
cool. The resulting adhesion promoters are hereafter
referred as AP#2 and AP#3.
EXAMPLE 3
A preferred adhesion promoter was produced via the
same method as described in Example 2 but in lieu of the
tall oil fatty acid blend either DIACID® 1550 (a tall oil
fatty acid-acrylic acid adduct commercially available
from Westvaco, Inc.) or a tall oil fatty acid modified
with fumaric acid was used. The range of ratios of
DIACID® 1550 to JONCRYL® 680 to polyamine blend was
80:40:100 to 120:30:100 by weight. The resulting
adhesion promoters are hereafter referred to as AP#4 and
AP#5. The ratio of fumarated tall oil fatty acid (15
parts by weight fumaric acid per 100 parts of weight tall
oil fatty acid reacted at 200°C) to JONCRYL® 680 to
polyamine blend was 80:40:120. The resulting adhesion
promoter is hereafter referred to as AP#6.
EXAMPLE 4
A preferred adhesion promoter was produced in the
same reaction flask via the following method. One
hundred parts by weight of the polyamine blend used in
Example 2 was charged and heated to 100-120°C. One
hundred parts by weight of crushed tall oil rosin
containing less than 10% tall oil fatty acids were slowly
added to the flask while agitating the polyamine blend.
The addition rate was adjusted in such a way that enough
time was allowed for the added rosin to form the
polyamine salt and the formation of big clumps of
agglomerated rosin could be avoided. Heating was resumed
to 150°C when 30 parts by weight of JONCRYL® 680 (a
styrene-acrylic resin manufactured by S.C.Johnson, Inc.)
were slowly added and heating to 230-250°C was resumed.
After 6 hours reaction time at this temperature the
product was allowed to cool to room temperature, at which
time 100 parts of diethylene glycol were added in order
to lower the viscosity of the adhesion promoter. The
resulting polyamidoamine adhesion promoter is hereafter
referred to as AP# 7.
EXAMPLE 5
Adhesion promoters were produced via the same method
noted above but in lieu of JONCRYL® 680 other styrene-acrylic
acid copolymers manufactured by S.C. Johnson,
Inc. (JONCRYL® resins), by Morton International (MOREZ®
resins), by Air Products (VANCRYL® resins), by Westvaco
(JONREZ® resins), and other manufacturers of similar
alkali-soluble acrylic resins were used in combination
with polyamines.
EXAMPLE 6
This example illustrates the invention methods
utilizing the adhesion promoters produced in Examples 1-5
in anionic emulsions prepared with a sodium soap of tall
oil (M28B) which were combined with granitic aggregate
from Georgia. An emulsion was prepared from Amoco EB-20
asphalt at 65% asphalt residue using 0.8% tall oil soap
(based on the weight of the emulsion) at pH 11.5. The
emulsion was allowed to cool to 140°F at which
temperature the adhesion promoter (generally 0.3% based
on the weight of the emulsion) was added to the emulsion
and held at this temperature for at least one hour. Then
it was mixed with aggregate retained on sieve openings of
2.83 mm or 1.19 mm (U.S. standard sieve No. 8 or 16).
Sufficient emulsion was used to
achieve a uniform coating of the aggregate. The mixes
were allowed to dry for two days at ambient temperature.
To determine the efficiency of the methods utilizing
the respective adhesion promoters the cured mixes were
placed in a basket which was introduced into boiling
water for ten minutes. After the basket was removed, the
aggregate was spread on a clean paper towel and allowed
to cool. The percent of retained asphalt coat on the
aggregate was judged visually after placing the sample in
a shallow glass pan filled with cold water and by
illuminating the coated aggregate surfaces with a 60 watt
lamp. The evaluation results are listed in Table I
below.
Evaluation of Adhesion Promoters with Anionic Asphalt Emulsion and Granite |
Asphalt: Amoco EB-20, 65% Asphalt Residue |
Emulsifier: Tall oil (M28B), 0.8%, pH 11.5 |
Aggregate: Granite (Georgia) passing 4.76 mm (No. 4) sieve, retained on 2.38 mm or 1.19 mm (No. 8 or 16) sieve |
Additive | Composition | % Dosage | % Coating |
| | | Before Boiling | After Boiling |
AP#1 | JONCRYL® 678-Amine Blend (50:50)/DEG (100) | 0.3 | 100 | 95 |
AP#2 | L-5-JONCRYL® 680-Amine Blend (100:50:100) | 0.3 | 100 | 95 |
AP#3 | L-5-JONCRYL® 680-Amine Blend (75:75:100) | 0.3 | 100 | 95 |
AP#4 | DIACID® 1550-JONCRYL® 680-Amine Blend (80:40:100) | 0.3 | 100 | 95 |
AP#5 | DIACID® 1550-JONCRYL® 680-Amine Blend (120:30:100) | 0.3 | 100 | 95 |
AP#6 | TRIACID® JONCRYL® 680-Amine Blend (80:40:120) | 0.3 | 100 | 95 |
AP#7 | Rosin-JONCRYL® 680-Amine Blend (120:30:100) | 0.3 | 100 | 95 |
Controls | | 0 | 100 | 0 |
AP#8 | L-5-Triethylene teramine (162.5:100) | 0.3 | 100 | 30 |
AP#9 | L-5-Amine Blend (150:100) | 0.3 | 100 | 40 |
AP#10 | Tallow triamine | 0.3 | Emulsion broke | - |
AP#11 | TRIACID® - Amine Blend (100:100) | 0.3 | 100 | 40 |
The results noted in Table I clearly show the
increased efficiency of the methods utilizing the novel
adhesion promoters disclosed herein, especially when
compared to conventional adhesion promoters such as tall
oil- or modified tall oil-based polyamine condensates or
tallow polyamines.
EXAMPLE 7
Using the evaluation procedures described in Example
6 above, a series of tests were conducted to show the
efficiency of the adhesion promoters of this invention
prepared from MOREZ® acrylic resins (manufactured by
Morton International) and evaluated in an emulsion
prepared of Exxon 125/150 penetration asphalt in
combination with granite from South Carolina. The
evaluation results are listed in Table II below.
Evaluation of Adhesion Promoters in Anionic Asphalt Emulsions in Combination with Granite |
Asphalt: Exxon 125/150 penetration Asphalt, 65% Asphalt Residue |
Emulsifier: Tall oil (M28B), 0.8%, pH 11.5 |
Aggregate: Granite (South Carolina), Retained on 12.7 mm sieve (½" U.S. Standard sieve) |
Adhesion | Composition | % Dosage | % Coating |
| | | Before Boiling | After Boiling |
AP#12 | MOREZ® 300-Amine Blend (60:50)/DEG (100) | 0.3 | 100 | 90 |
AP#13 | MOREZ® 300-Amine Blend (40:50)/DEG (100) | 0.3 | 100 | 90 |
AP#14 | L-5-MOREZ® 300-Amine Blend (100:50:100) | 0.3 | 100 | 95 |
AP#14 | L-5-MOREZ® 300-Amine Blend (100:50:100) | 0.25 | 100 | 80 |
AP#14 | L-5-MOREZ® 300-Amine Blend (100:50:100) | 0.2 | 100 | 80 |
AP#15 | L-5-MOREZ® 300-Amine Blend (150:30:100) | 0.3 | 100 | 95 |
AP#16 | L-5-JONCRYL® 680-Amine Blend (120:30:100) | 0.3 | 100 | 95 |
Control | | 0 | 100 | 0 |
This example shows the efficiency of methods
utilizing styrene-acrylic resin-derived polyamine
condensates and of tall oil fatty acid/acrylic resin-derived
polyamine condensates as adhesion promoters.
EXAMPLE 8
Using the evaluation procedures described in Example
6 above, a series of tests were conducted to show the
efficiency of the adhesion promoters of this invention
containing anionic SBR latex (Butonal NS-120,
manufactured by BASF) and evaluated in an emulsion
prepared of Exxon 125/150 penetration asphalt in
combination with granite from South Carolina. The
evaluation results are listed in Table III below.
Evaluation of Adhesion Promoters in Polymers Latex-modified Asphalt Emulsions in Combination with Granite |
Asphalt: Exxon 125/150 penetration Asphalt, 65% Asphalt Residue |
Polymer: 3% (as is) SBR-Latex (Butonal NS-120, BASF) |
Emulsifier: Tall oil (M28B), 0.8%, pH 11.5 |
Aggregate: Granite (South Carolina), Retained on 12.7 mm sieve (½" U.S. Standard Sieve) |
Adhesion Promoter | Composition | % Dosage | % Coating |
| | | Before Boiling | After Boiling |
AP#16 | L-5-JONCRYL® 680-Amine Blend (120:30:100) | 0.3 | 100 | 95 |
AP#16 | L-5-JONCRYL® 680-Amine Blend (120:30:100) | 0.25 | 100 | 90 |
AP#17 | L-5-MOREZ® 300-Amine Blend (120:30:100) | 0.3 | 100 | 95 |
AP#15 | L-5-MOREZ® -Amine Blend (150:30:100) | 0.3 | 100 | 90 |
AP#15 | L-5-Amine Blend (150:30:100) | 0.25 | 100 | 95 |
AP#18 | C-3B-MOREZ® 300-Amine Blend (150:30:100) | 0.25 | 100 | 95 |
Controls | | 0 | 100 | 10 |
AP#19 | INDULIN AS-Special | 0.3 | 100 | 60 |
AP#19 | INDULIN AS-Special | 0.25 | 100 | 30 |
This example indicates that methods utilizing polyamidoamines
derived from tall oil/acrylic resin blends are
more efficient at promoting adhesion than conventional tall
oil-derived amidoamines.
EXAMPLE 9
Using the evaluation procedures described in Example 6
above, a series of tests were conducted to show the efficiency of
the novel adhesion promoters of this invention when utilized with
quartzite river gravel (which is notorious for asphalt-stripping).
The evaluation results are listed in Table IV below.
Evaluation of Adhesion Promoters in Polymer Latex-Modified Anionic Asphalt Emulsions in Combination with Ouartzite |
Asphalt: Exxon 125/150 penetration Asphalt, 65% Asphalt Residue |
Polymer: 3% (as is) SBR-Latex (Butonal NS-120, BASF) |
Emulsifier: Tall oil (M28B), 0.8%, pH 11.5 |
Aggregate: Quartzite (River Gravel, South Carolina), retained on 4.76 mm sieve (No. 4 U.S. Standard Sieve) |
Adhesion Promoter | Composition | % Dosage | % Coating |
| | | Before Boiling | After Boiling |
AP#16 | L-5-JONCRYL® 680-Amine Blend (120:30:100) | 0.3 | 100 | 70 |
AP#16 | L-5-JONCRYL® 680-Amine Blend (120:30:100) | 0.25 | 100 | 40 |
AP#14 | L-5-MOREZ® 300-Amine Blend (120:50:100) | 0.3 | 100 | 50 |
AP#14 | L-5-MOREZ® -Amine Blend (150:50:100) | 0.25 | 100 | 40 |
AP#18 | C-3B-MOREZ® 300-Amine Blend (150:30:100) | 0.3 | 100 | 60 |
Controls | | 0 | 100 | 10 |
AP#19 | INDULIN AS-Special | 0.3 | 100 | 40 |
AP#19 | INDULIN AS-Special | 0.25 | 100 | 20 |
This example shows the improved performance of methods
utilizing polyamidoamines derived from tall oil/styrene-acrylic
resin blends vis-a-vis conventional tall oil-based amidoamines.
EXAMPLE 10
This example shows the improved performance of the
invention adhesion promoters with quartzite aggregate which
is known to strip asphalt from its surface when exposed to
water.
Using the evaluation procedures described in Example 6
above, a series of tests were conducted to show the efficiency of
the novel adhesion promoters of this invention when utilized with
quartzite aggregate (which is known to strip asphalt from its
surface when exposed to water). The evaluation results are listed
in Table V below.
Evaluation of Adhesion Promoters in Anionic Emulsions in Combination with Quartzite |
Asphalt: Amoco EB-20 Asphalt (A), 65% Asphalt Residue Exxon 125/150 Penetration Asphalt (B), 65% Asphalt Residue |
Emulsifier: Tall Oil (M28B), 0.8%, pH 11.5 |
Aggregate: Quarzite (River Gravel, South Carolina), retained on 12.7 mm sieve (½" U.S. Standard Sieve) |
Adhesion Promoter | Composition | % Dosage (Asphalt) | % Coating |
| | | Before Boiling | After Boiling |
AP#20 | L-5-JONCRYL® 680-Amine Blend (100:50:87.5) | 0.3 (A) | 100 | 85 |
AP#16 | L-5-JONCRYL® 680-Amine Blend (120:30:100) | 0.3 (A) | 100 | 85 |
AP#16 | L-5-JONCRYL® 680-Amine Blend (120:30:100) | 0.3 (B) | 100 | 85 |
AP#13 | MOREZ® 300-Amine Blend (40:50)/DEG (100) | 0.3 (B) | 100 | 80 |
AP#21 | MOREZ® 100-Amine Blend (50:50)/DEG (100) | 0.3 (B) | 100 | 80 |
AP#9 | L-5 amine Blend (150:100) | 0.3 (A) | 100 | 10 |
AP#22 | INDULIN AS-101 | 0.3 (A) | 100 | 20 |
AP#22 | INDULIN AS-101 | 0.3 (B) | 100 | 20 |
Control | | 0 (A,B) | 100 | 0 |
This Example shows the improved performance of
methods utilizing polyamidoamines obtained from styrene-acrylic
resins or tall oil fatty acid/styrene-acrylic
resin blends when compared to conventional tall oil fatty
acid-derived amidoamines.
It is clear that the novel adhesion promoter
compositions taught herein achieved superior results when
compared to conventional adhesion promoters used for
asphalt/aggregate compositions. Many modifications and
variations of the present invention will be apparent to
one skilled in the art in light of the above teaching.
It is understood therefore that the scope of the
invention is not to be limited by the foregoing
description, but rather is to be defined by the claims
appended hereto.